EP3103768A1 - Reduziertes graphenoxid, seine derivate, herstellungsverfahren und tinte davon - Google Patents

Reduziertes graphenoxid, seine derivate, herstellungsverfahren und tinte davon Download PDF

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Publication number
EP3103768A1
EP3103768A1 EP15275150.9A EP15275150A EP3103768A1 EP 3103768 A1 EP3103768 A1 EP 3103768A1 EP 15275150 A EP15275150 A EP 15275150A EP 3103768 A1 EP3103768 A1 EP 3103768A1
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Prior art keywords
graphene oxide
cyanide
oxide derivative
derivative
reduced graphene
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EP15275150.9A
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English (en)
French (fr)
Inventor
Salvatore Zarra
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Provenance Asset Group LLC
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Nokia Technologies Oy
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Priority to EP15275150.9A priority Critical patent/EP3103768A1/de
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Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/23—Oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present disclosure relates to the field of reduced graphene oxide, reduced graphene oxide derivatives and associated apparatus.
  • the disclosure concerns a process for the preparation of reduced graphene oxide or a reduced graphene oxide derivative and associated apparatus.
  • Graphene has attracted great interest for its excellent mechanical, electrical, thermal and optical properties. It is typically produced by micro-mechanical exfoliation of highly ordered pyrolytic graphite, epitaxial growth, chemical vapour deposition, and by the reduction of graphene oxide.
  • Graphene oxide has two important characteristics: (1) it is typically produced using inexpensive graphite as the raw material by cost-effective methods in a high yield; and (2) it is typically highly hydrophilic and can form stable aqueous colloids that facilitates the assembly of macroscopic structures. Both of these characteristics are important to large scale uses of graphene.
  • rGO Reduction of GO
  • rGO contains defects created by the reduction process. These defects can be highly detrimental to the electrical conductivity of rGO. Also the removal of oxygen containing groups during the reduction process typically renders the obtained rGO not easily dispersible. This is a disadvantage when rGO is used in printable inks, and a surfactant is often required to aid the dispersibility of rGO. The presence of a surfactant often affects the properties of the printed material, thus it is desirable to be able to provide a printable ink comprising rGO that does not require the addition of a surfactant.
  • One or more aspects/embodiments of the present disclosure may or may not address one or more of these issues.
  • the present invention provides a process for preparing a reduced graphene oxide or a reduced graphene oxide derivative, which process comprises reducing graphene oxide, or a graphene oxide derivative, with a reducing agent, wherein the process is conducted at a pH of less than about 4.
  • the process further comprises the step of forming the graphene oxide derivative prior to reduction by reacting graphene oxide with a functionalising compound.
  • the present invention also provides a process for preparing a reduced graphene oxide derivative comprising the steps of:
  • the graphene oxide, or graphene oxide derivative is typically present at a concentration of from about 0.1 to about 50 mg/mL, or from about 1 to about 30 mg/mL, or from about 5 to about 20 mg/mL, such as from about 10 to about 15 mg/mL.
  • the ratio of graphene oxide, or graphene oxide derivative to reducing gent is typically from about 20:1 to about 1:10, or from about 10:1 to about 1:2, or from about 5:1 to about 1:1.
  • the reducing agent is typically an organic compound, such as an organic acid.
  • the reducing agent is ascorbic acid, or a salt, solvate or derivative thereof.
  • the reducing agent is citric acid, or a salt, solvate or derivative thereof.
  • the process is conducted at a pH of less than about 1 using ascorbic acid as the reducing agent. In a preferred aspect of the invention, the process is conducted at a pH of about 0 using ascorbic acid or citric acid as the reducing agent.
  • graphene oxide we mean any oxidised form of graphene; for example, graphene oxide that has been prepared by oxidising and exfoliating graphite.
  • graphene oxide encompasses graphene oxide that may comprise impurities remaining from the process used to prepare the graphene oxide and/or the processes described herein.
  • the graphene oxide may also comprise solvent and/or suspended or dissolved compounds present during the preparation of the graphene oxide.
  • graphene oxide derivative we mean any form of graphene oxide wherein at least 10%, such as at least 40% or at least 60% of the oxygen containing groups of the graphene oxide have been covalently functionalised, for example, through reaction of hydroxyl groups present on GO and nitrile or amine containing functionalising compounds such as through the Pinner reaction.
  • the functionalising compound is a compound that may covalently react with the hydroxyl groups present on the GO.
  • the functionalising compound is a compound that may covalently react with epoxide or carboxylic acid groups present on the GO or with the aromatic basal plane of GO.
  • the functionalising compound is a compound of formula I, R-X (I) wherein R represents C 1-12 alkyl, C 2-12 alkenyl, C 2-12 alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, each of which is substituted or un-substituted;
  • R a and R b independently represent hydrogen or a C 1-6 alkyl group.
  • the compound of formula I is a polymer containing one or more X substituents, wherein X is as defined above.
  • Polymers that may be mentioned in this respect include polyesters (e.g. polyhydroxyalkanoates or polyethylene terephthalates), polyethers (e.g. polyethylene glycol (PEG) or polypropylene glycol (PPG)), polyolefins (e.g. polyethylene or polypropylene) and other polymers (e.g. poly(vinyl chloride) or an acrylate polymer (such as poly(methyl methacrylate) and polyacrylonitrile)).
  • Each polymer may, as indicated above, contain one or more X substituents covalently bonded to the polymer (e.g. a polyether which contains one or more additional nitrile substituents bonded to each polyether molecule), or the one or more X substituents may be part of the repeating polymer structure (e.g. polyacrylonitrile).
  • R groups in compounds of formula I include halogen atoms and C 1-4 alkyl groups.
  • X is -N(R a )R b b (preferably wherein at least one of R a and R b is hydrogen).
  • the compound of formula I may be first converted into a different chemical form (e.g. by converting the X component into a different functional group in situ ) before it is reacted with the GO.
  • the compound of formula I is an aryl amine or heteroaryl amine
  • the amine group may be converted into a diazonium group (e.g. to facilitate an electrophilic substitution reaction) prior to reaction with the GO.
  • the diazonium group may be formed by any method known to the person skilled in the art (e.g. using nitrous acid in the presence of a strong acid).
  • the compound of formula I may be reacted with the hydroxyl groups present on the GO by any means known to the skilled person.
  • the functionalising compound is selected from the group consisting of substituted or un-substituted C 1-12 alkyl cyanide, heteroalkyl cyanide, cycloalkyl cyanide, heterocycloalkyl cyanide, C 2-12 alkenyl cyanide, heteroalkenyl cyanide, C 2-12 alkynyl cyanide, heteroalkynyl cyanide, aryl cyanide, heteroaryl cyanide, a C 1-12 alkyl amine, C 2-12 alkenyl amine, an aryl amine and a heteroaryl amine.
  • Optional substituents that may be mentioned in this respect include halogen atoms and C 1-4 alkyl groups.
  • the functionalising compound is an optionally substituted heteroaryl amine, or preferably an optionally substituted heteroaryl cyanide.
  • the functionalising compound is a compound of formula I in which X represents -CN.
  • C 1-q alkyl groups (where q is the upper limit of the range) defined herein may be straight-chain or, when there is a sufficient number of carbon atoms, be branched-chain.
  • C 2-q alkenyl groups and C 2-q alkynyl groups may be straight-chain or, when there is a sufficient number of carbon atoms, be branched-chain.
  • Cycloalkyl groups that may be mentioned may be monocyclic or bicyclic alkyl groups, which cycloalkyl groups may further be bridged (so forming, for example, fused ring systems such as three fused cycloalkyl groups).
  • Such cycloalkyl groups may be saturated or unsaturated containing one or more double or triple bonds (forming for example a cycloalkenyl or cycloalkynyl group). Substituents may be attached at any point on the cycloalkyl group. Further, where there is a sufficient number (i.e. a minimum of four) such cycloalkyl groups may also be part cyclic.
  • a heteroalkyl group is an alkyl group in which at least one (e.g. one) of the carbon atoms in the backbone has been replaced with a heteroatom (preferably selected from N, O and S). At least one carbon atom remains in the backbone in addition to the one or more heteroatoms.
  • Such heteroalkyl groups may be straight-chain or, when there is a sufficient number of atoms, be branched-chain.
  • Heteroalkenyl and heteroalkynyl groups are corresponding variants of alkenyl groups and alkynyl groups, i.e. variants in which at least one (e.g. one) of the carbon atoms in the backbone has been replaced with a heteroatom (preferably selected from N, O and S), but at least two adjacent carbon atoms remain thus affording the required unsaturation.
  • Heterocycloalkyl groups that may be mentioned include non-aromatic monocyclic and bicyclic heterocycloalkyl groups in which at least one (e.g. one to four) of the atoms in the ring system is other than carbon (i.e. a heteroatom), and in which the total number of atoms in the ring system is from five to ten. Such heterocycloalkyl groups may also be bridged. Further, such heterocycloalkyl groups may be saturated or unsaturated containing one or more double and/or triple bonds, forming for example a heterocycloalkenyl (where q is the upper limit of the range) or a heterocycloalkynyl group.
  • Aryl groups that may be mentioned include C 6-10 aryl groups. Such groups may be monocyclic or bicyclic and have from 6 to 10 ring carbon atoms, in which at least one ring is aromatic.
  • C 6-10 aryl groups include phenyl, naphthyl and the like, such as 1,2,3,4-tetrahydronaphthyl. The point of attachment of aryl groups may be via any atom of the ring system. However, when aryl groups are bicyclic, they are linked to the rest of the molecule via an aromatic ring.
  • heteroaryl when used herein refers to an aromatic group containing one or more heteroatom(s) (e.g. one to four heteroatoms) preferably selected from N, O and S.
  • Heteroaryl groups include those which have from 5 to 10 members and may be monocyclic or bicyclic, provided that at least one of the rings is aromatic (so forming, for example, a mono- or bicyclic heteroaromatic group).
  • heteroaryl groups are bicyclic or tricyclic, they are linked to the rest of the molecule via an aromatic ring.
  • Heteroaryl groups that may be mentioned include pyrimidine, pyrazine, pyridazine and, preferably, pyridine.
  • halo when used herein, include fluoro, chloro, bromo and iodo.
  • forming the graphene oxide derivative is performed in the presence of a strong acid.
  • suitable inorganic acids include, but are not limited to, hydrochloric acid (HCl), nitric acid (HNO 3 ), phosphoric acid (H 3 PO 4 ), sulphuric acid (H 2 SO 4 ), boric acid (H 3 BO 3 ), hydrofluoric acid (HF), hydrobromic acid (HBr), and perchloric acid (HClO 4 ).
  • suitable organic acids include, but are not limited to, halogenated acetic acid (e.g. trifluoracetic acid or trichloroacetic acid), methane sulfonic acid, trifluoromethane sulfonic acid, p-toluenesulfonic acid and aminomethylphosphonic acid.
  • the contact time between the graphene oxide, the functionalising compound and strong acid for forming the graphene oxide derivative will typically be from about 0.5 seconds to about 24 hours, e.g. from about 10 minutes to about 2 hours, such as about 1 hour.
  • the contact time between the graphene oxide derivative mixture, obtained by contacting the graphene oxide, the functionalising compound and strong acid, and the reducing agent will typically be from about 0.5 seconds to about 24 hours, e.g. from about 1 second to about 10 minutes, such as 5 minutes.
  • the contact time may vary depending on whether the contacting is being done on a laboratory scale or on a larger industrial scale and would be able to adjust the contacting times accordingly.
  • the method of the disclosure may be carried out at atmospheric, sub- or super-atmospheric pressure, preferably atmospheric pressure.
  • the method of the present disclosure may be conducted at any temperature. Typically, the method of the disclosure is typically conducted at about room temperature (i.e. about 25°C). However, it is to be understood that the method may be conducted at higher or lower temperatures, such as from about -40°C to about 200°C, for example from about 0°C to about 100°C or from about 20°C to about 60°C.
  • the functionalising reactions described herein are preferably conducted at about room temperature.
  • the reduction reactions may, however, be conducted at a different temperature (e.g. at from about 40°C to about 70°C (e.g. about 60°C)). It would be appreciated by the skilled person that the reaction temperature may depend on the type of reaction being performed and the functional groups present and would modify the temperature ranges accordingly.
  • the components of the process are typically mixed together to facilitate the reaction process.
  • Effective mixing techniques include, but are not limited to, shaking and/or stirring.
  • a chemical reactor may be equipped with a stirring unit to enable the solutions to be mixed on a large scale.
  • the process of forming the graphene oxide derivative and reducing the graphene oxide derivative is conducted in a "one-pot" procedure.
  • one-pot we mean that the graphene oxide derivative is not isolated from the reaction before being reduced.
  • One-pot procedures may be advantageous because, if the Pinner reaction is used for the functionalisation, for example, there is no need to isolate the graphene oxide derivatives or change the pH of the crude reaction mixture before introducing the ascorbic acid or other reducing agent.
  • the pH is typically less than about 4, such as less than about 2, or less than about 1.
  • the pH may be from about 0 to about 3, or from about 0 to about 2, or from about 0 to about 1.
  • the process of the invention is conducted in the presence of an aqueous solvent system.
  • the process of the invention may be conducted in the presence of water.
  • the additional solvent is a polar organic solvent, such as methanol or ethanol.
  • composition or formulation or component being described must contain the listed ingredient(s) but may optionally contain one or more additional ingredients.
  • the term consisting essentially of or consists essentially of we mean that the composition or formulation or component being described must contain the listed ingredient(s) and may also contain other small (for example up to 5% by weight, or up to 1% by weight or up to 0.1% by weight) ingredients, provided that any additional ingredients do not affect the essential properties of the composition, formulation or component.
  • consisting of or consists of we mean that the composition, formulation or component being described must contain the listed ingredient(s) only with no detectable amounts of other ingredients.
  • the present invention also provides a reduced graphene oxide or reduced graphene oxide derivative obtainable by the process of the invention described herein.
  • the reduced graphene oxide or reduced graphene oxide derivative prepared by the process of the invention may be dispersed into organic solvents without the need for any additional surfactants or other additives.
  • solvents in which the reduced graphene oxide or reduced graphene oxide derivative may be dispersed include, but are not limited to, dimethylformamide (DMF), water, N-methyl-2-pyrrolidone (NMP), chloroform, toluene, chlorobenzenes, or ethylene glycol. Mixtures of solvents might be used too for the dispersion reduced graphene oxide or reduced graphene oxide derivatives.
  • the reduced graphene oxide or reduced graphene oxide derivative may be used in an ink, such as a printable ink, formulated with or without other suitable additives, for the deposition on a suitable substrate, either flexible or rigid, by using any technique including, but not limited to, gravure, roll-to-roll, screen, inkjet and flexographic printing, drop casting, filtration, spin coating, dip coating and spraying.
  • the present invention also provides an ink comprising the reduced graphene oxide or reduced graphene oxide derivative product of the process of the invention.
  • an electronic component including a graphene oxide composite obtained from the method disclosed herein is provided.
  • an apparatus for processing an aqueous solution comprising graphene oxide as defined previously wherein the apparatus is configured to perform any of the methods described herein.
  • a computer recordable medium comprising a computer programme code stored thereon, the computer recordable medium and computer programme code being configured to, when run on at least one processor of a processing apparatus, cause the processing apparatus to provide for performing any of the methods described herein.
  • any mentioned apparatus/device and/or other features of particular mentioned apparatus/device may be provided by apparatus arranged such that they become configured to carry out the desired operations only when enabled, e.g. switched on, or the like. In such cases, they may not necessarily have the appropriate software loaded into the active memory in the non-enabled (e.g. switched off state) and only load the appropriate software in the enabled (e.g. on state).
  • the apparatus may comprise hardware circuitry and/or firmware.
  • the apparatus may comprise software loaded onto memory.
  • Such software/computer programs may be recorded on the same memory/processor/functional units and/or on one or more memories/processors/functional units.
  • a particular mentioned apparatus/device may be pre-programmed with the appropriate software to carry out desired operations, and wherein the appropriate software can be enabled for use by a user downloading a "key", for example, to unlock/enable the software and its associated functionality.
  • Advantages associated with such embodiments can include a reduced requirement to download data when further functionality is required for a device, and this can be useful in examples where a device is perceived to have sufficient capacity to store such pre-programmed software for functionality that may not be enabled by a user.
  • any mentioned apparatus/circuitry/elements/processor may have other functions in addition to the mentioned functions, and that these functions may be performed by the same apparatus/circuitry/elements/processor.
  • One or more disclosed aspects may encompass the electronic distribution of associated computer programs and computer programs (which may be source/transport encoded) recorded on an appropriate carrier (e.g. memory, signal).
  • any "processing apparatus" described herein can comprise a collection of one or more individual processors/processing elements that may or may not be located on the same circuit board, or the same region/position of a circuit board or even the same device. In some embodiments one or more of any mentioned processors may be distributed over a plurality of devices. The same or different processor/processing elements may perform one or more functions described herein.
  • processors and memory may comprise a computer processor, Application Specific Integrated Circuit (ASIC), field-programmable gate array (FPGA), and/or other hardware components that have been programmed in such a way to carry out the inventive function.
  • ASIC Application Specific Integrated Circuit
  • FPGA field-programmable gate array
  • the present disclosure includes one or more corresponding aspects, example embodiments or features in isolation or in various combinations whether or not specifically stated (including claimed) in that combination or in isolation.
  • Corresponding means for performing one or more of the discussed functions are also within the present disclosure.
  • L-ascorbic acid (2g) was added to the other half of the reaction mixture, the one which was not subjected to work-up, and the reaction was stirred vigorously at 60°C for 5 hours at pH around 0. After 5 hours the crude reaction mixture was filtered whilst still hot through a glass frit filter using vacuum filtration. The resulting solid was then washed with copious amounts of deionised water until the pH of the filtrate was 7. The solid was then washed with acetone and isopropanol. The final product (0.170g) was then dried under vacuum.
  • the reduced graphene oxide derivative prepared in Example 1 was dispersed in DMF (1 mg/mL) to provide a reduced graphene oxide derivative ink.
  • the ink was drop cast onto different geometries of printed silver electrodes in order to ascertain the electrical resistance.
  • a reduced graphene oxide ink prepared by dispersing in DMF (1 mg/mL) reduced graphene oxide powder obtained by reducing a graphene oxide dispersion with L-ascorbic acid at pH around 4, was also drop cast and its electrical resistance tested.
  • the graphene oxide was reduced using the same reduction method as used in the process of the invention except for the use of a higher pH. This higher pH affords a material which is less conductive (Table 1) and dispersible than the one obtained when the graphene oxide derivative of the graphene oxide are reduced at pH lower than 4.
  • FIG. 1 shows the test electrode layouts 1 designated by A, B and C, as well as test number as explained below.
  • Electrode arrangement A comprises two columns of interdigitated electrodes with 400 micrometer gaps.
  • Electrode arrangement B comprises two columns of interdigitated electrodes with 300 micrometer gaps.
  • Electrode arrangement C comprises column electrodes with a 5mm gap.
  • the sheet resistance of the reduced graphene oxide derivative, reduced at very low pH, around 0, can be estimated to be ca. 400 Ohm per square.
  • the reduced graphene oxide obtained at pH around 4, displays a sheet resistance approximately 3 orders of magnitude higher.
  • Figure 2 shows an apparatus 20 for processing an aqueous solution using the methods described herein, the apparatus 20 includes a processor and memory, shown together as 21, for controlling a chemical processing apparatus.
  • Figure 3 shows a computer readable medium comprising a CD-ROM with computer program code thereon for execution on said processor and memory 21.
  • Figure 4 shows an electrical component, such as a sensor 40, including the reduced graphene oxide obtained by the methods described herein.

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EP15275150.9A 2015-06-09 2015-06-09 Reduziertes graphenoxid, seine derivate, herstellungsverfahren und tinte davon Withdrawn EP3103768A1 (de)

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Cited By (2)

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CN109183123A (zh) * 2018-07-16 2019-01-11 西安理工大学 石墨烯/氧化石墨烯电解液中钛及钛合金阳极氧化方法
US10840505B2 (en) 2015-09-18 2020-11-17 Nokia Technologies Oy Apparatus and method of providing an apparatus for use as a power source

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10840505B2 (en) 2015-09-18 2020-11-17 Nokia Technologies Oy Apparatus and method of providing an apparatus for use as a power source
CN109183123A (zh) * 2018-07-16 2019-01-11 西安理工大学 石墨烯/氧化石墨烯电解液中钛及钛合金阳极氧化方法
CN109183123B (zh) * 2018-07-16 2020-07-24 西安理工大学 石墨烯/氧化石墨烯电解液中钛及钛合金阳极氧化方法

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